U.S. patent number 3,894,059 [Application Number 05/355,437] was granted by the patent office on 1975-07-08 for process for the oxidation of olefines.
This patent grant is currently assigned to Petrocarbon Developments Limited. Invention is credited to Thillyampalam Selvaratnam.
United States Patent |
3,894,059 |
Selvaratnam |
July 8, 1975 |
Process for the oxidation of olefines
Abstract
Processes are provided for the oxidation of olefinically
unsaturated compounds to oxirane compounds, vic-glycols and
vic-halohydrins in which the olefinically unsaturated compound,
carbon dioxide water and hypohalite are brought into intimate
contact so as to form vic-halohydrin, and if desired, exposing the
vic-halohydrin to aqueous bicarbonate so as to form oxirane
compound and/or vic-glycol. Bicarbonate is formed as by-product in
the production of vic-halohydrin and this bicarbonate may be used
to convert the vic-halohydrin to oxirane compound or vic-glycol.
Also carbon dioxide is formed as by-product during the conversion
and this is advantageously used to provide carbon dioxide required
for the production of the vic-halohydrin. Similarly, the hypohalite
is conveniently formed by electrolysis of metal halide derived as
by-product of the conversion of vic-halohydrin to oxirane compound
or vic-glycol.
Inventors: |
Selvaratnam; Thillyampalam
(Sale, EN) |
Assignee: |
Petrocarbon Developments
Limited (Manchester, EN)
|
Family
ID: |
10150169 |
Appl.
No.: |
05/355,437 |
Filed: |
April 30, 1973 |
Foreign Application Priority Data
|
|
|
|
|
May 3, 1972 [GB] |
|
|
20696/72 |
|
Current U.S.
Class: |
549/522; 549/541;
568/859; 205/499; 423/424; 568/850 |
Current CPC
Class: |
C07C
29/66 (20130101); C07D 301/26 (20130101); C07C
29/66 (20130101); C07C 31/36 (20130101); C07C
29/106 (20130101); C07C 31/202 (20130101); C07C
29/106 (20130101); C07C 31/205 (20130101) |
Current International
Class: |
C07C
29/00 (20060101); C07C 29/66 (20060101); C07D
301/00 (20060101); C07D 301/26 (20060101); C07d
001/04 (); C07d 001/12 (); C07d 001/14 () |
Field of
Search: |
;260/348.6 ;204/95 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Milestone; Norma S.
Attorney, Agent or Firm: Browdy and Neimark
Claims
I claim:
1. A process for the production of an oxirane compound comprising
the steps of:
1. reacting at a temperature not greater than 10.degree.C. but
above the freezing temperature of the system an olefinically
unsaturated compound, carbon dioxide, water and a hypohalite in
quantities sufficient to produce an aqueous product mixture
comprising substantially equimolar quantities of bicarbonate and
vic-halohydrin; and
2. heating at least a portion of said aqueous product mixture to a
temperature resulting in reaction together of said vic-halohydrin
and said aqueous bicarbonate to form an oxirane compound.
2. A process according to claim 1 in which at least part of the
carbon dioxide used in said reacting step comprises carbon dioxide
evolved from the reaction mixture during said heating step.
3. A process according to claim 1 in which the hypohalite is a
metal hypohalite.
4. A process according to claim 1 in which the bicarbonate is metal
bicarbonate and the hypohalite is metal hypohalite formed by
electrolysis of aqueous metal halide formed during said heating
step.
5. A process according to claim 1 in which said heating step is
carried out at a temperature of from 50.degree.C to
115.degree.C.
6. A process according to claim 1 in which said heating step is
carried out at a pressure of from 0.5 to 2.0 Kg/cm.sup.2
absolute.
7. A process according to claim 1 in which oxirane compound formed
as a result of reaction between vic-halohydrin and aqueous
bicarbonate is stripped from the reaction mixture with the aid of
carbon dioxide formed in situ as a result of the reaction and/or
with steam and/or with olefinically unsaturated compound.
8. A process according to claim 1 in which the temperature is from
-15.degree.C to +10.degree.C.
9. A process according to claim 1 in which the temperature is from
+5.degree.C to +10.degree.C.
10. A process according to claim 1 in which the contacting of the
olefinically unsaturated compound, carbon dioxide, water and
hypohalite is carried out at a pressure of from 1.5 to 5.0
Kg/cm.sup.2 absolute.
11. A process according to claim 1 in which a substantially
equimolar gaseous mixture of the olefinically unsaturated compound
and the carbon dioxide is contacted with an aqueous solution of
hypohalite.
12. A process according to claim 11 in which the aqueous solution
contains from 2 to 5 wt percent of metal hypohalite.
13. A process according to claim 1 in which the olefinically
unsaturated compound and the carbon dioxide are contacted with an
aqueous solution containing up to 6 wt percent of metal
hypohalite.
14. A process according to claim 1 in which the hypohalite is
sodium hypochlorite.
15. A process according to claim 1 in which the olefinically
unsaturated compound is ethylene or propylene.
16. A process as claimed in claim 1 comprising the steps of:
i. forming an aqueous solution containing a metal hypohalite by
electrolysis of an aqueous solution of metal halide,
ii. intimately contacting an olefinically unsaturated compound and
carbon dioxide with the aqueous solution containing metal
hypohalite formed in step (i) so as to form an aqueous solution
containing substantially equimolar quantities of metal bicarbonate
and vic-halohydrin;
iii. heating at least a portion of said aqueous solution formed in
step (ii) to a temperature resulting in reaction together of
vic-halohydrin and aqueous metal bicarbonate contained in said
aqueous solution to form a product mixture comprising an oxirane
compound together with metal halide, carbon dioxide and water;
iv. separately recovering carbon dioxide, an aqueous solution of
metal halide and a product stream comprising oxirane compound from
the product mixture formed in step (iii);
v. recycling carbon dioxide from step (iv) for use in step (ii)
and
vi. recycling aqueous metal halide solution from step (iv) for
electrolysis in accordance with step (i).
17. A process according to claim 16 in which the concentration of
the aqueous metal halide subjected to electrolysis is adjusted to
within the range from 15 to 27 wt percent.
18. A process as claimed in claim 1 comprising the steps of:
i. electrolyzing an aqueous solution of a metal halide to form an
aqueous solution containing metal hypohalite and metal halide;
ii. contacting the aqueous solution formed in step (i) with carbon
dioxide and an olefinically unsaturated compound at a
superatmospheric pressure to form an aqueous product mixture
comprising substantially equimolar quantities of metal bicarbonate
and vic-halohydrin;
iii. raising the temperature of said aqueous product mixture formed
in step (ii) to effect reaction between the vic-halohydrin and
aqueous metal bicarbonate contained therein to form a product
mixture comprising oxirane compound, carbon dioxide and aqueous
metal halide;
iv. separately recovering oxirane compound, carbon dioxide and
aqueous metal halide from the product mixture formed in step (iii);
and
v. recycling aqueous metal halide recovered in step (iv) for
electrolysis according to step (i); and
vi. recycling carbon dioxide recovered in step (iv) for use as or
as part of the carbon dioxide requirement of step (ii).
Description
This invention relates to a process for the oxidation of
olefinically unsaturated compounds and especially for the
production of oxirane compounds, vic-glycols and
vic-halohydrins.
Oxirane compounds and particularly olefin oxides have hitherto been
commercially produced either by the so-called chlorhydrin process,
which requires the use of chlorine as a raw material, or by direct
oxidation of olefins using air, oxygen, peroxides or
hydroperoxides. At the present time, ethylene oxide is produced
almost entirely by the direct oxidation of ethylene with oxygen or
air over silver and other catalysts, the yield of ethylene oxide
being about 70 percent on ethylene, the balance going to carbon
dioxide. Currently, more than 80 percent of the production of
propylene oxide is by the chlorhydrin process, which has the
disadvantage of producing byproducts such as dichloropropane and
dichloro-isopropyl ether, which, apart from consuming costly
chlorine, have negligible commercial uses.
Another very important disadvantage of the chlorhydrin process is
that it produces large quantities of hot effluents containing
relatively small (3-5 percent) concentrations of alkali or alkaline
earth chloride, which are costly to treat for disposal or for
recycle of their chlorine content, and which are claimed to be
damaging to the environment. In recent years, propylene oxide is
being produced also by the capital intensive direct oxidation
process, which has the disadvantage of co-producing very large
quantities of by-products which cause fluctuations of market
stability. Epichlorhydrin continues to be produced only by the
chlorhydrin process, with all the disadvantages of by-products and
effluents.
According to one aspect of the present invention, there is provided
a process for the production of an oxirane and/or a vic-glycol
which comprises the steps of (a) forming a vic-halohydrin by
bringing into intimate contact an olefinically unsaturated
compound, carbon dioxide, water and a metal hypohalite, and (b)
converting vic-halohydrin formed in step (a) to oxirane compound
and/or vic-glycol by exposure of the vic-halohydrin to an aqueous
medium containing a metal bicarbonate.
The individual process comprising step (a) above forms a further
separate aspect of the present invention, and thus the present
invention also provides a process for the production of a
vic-halohydrin which comprises bringing into intimate contact an
olefinically unsaturated compound, carbon dioxide, water and a
hypohalite, and recovering vic-halohydrin from the product mixture
so formed.
The processes comprised by steps (a) and (b) are believed to
operate in accordance with the following equations (where X is
halogen, <C=C< represents the olefinically unsaturated
compound and for reasons of simplicity, the hypohalite is
represented as being one of a monovalent metal, indicated by M,
although other hypohalites such as ammonium hypohalite and
hypohalites of polyvalent metals may also be used): ##SPC1##
Overall, the production of oxirane compound and of vic-glycol may
be represented by the following equations: ##SPC2##
and the process for the production of oxirane compound and/or a
vic-glycol provided in accordance with the invention may be stated
as comprising the oxidation of an olefinically unsaturated compound
in the presence carbon dioxide with an aqueous medium containing
hypohalite ions, and where vic-glycol is required at the expense of
oxirane compound, hydrolyzing oxirane product of the oxidation.
The olefinically unsaturated compound may be a hydrocarbon for
example ethylene or propylene, or a substituted hydrocarbon, for
example allyl chloride. Thus, products which may be obtained by the
process of the invention include ethylene oxide, propylene oxide
and epichlorhydrin and the corresponding vic-glycols and
vic-chlorhydrins. The invention has particular economic
significance when applied to the oxidation of olefinically
unsaturated compounds having a small number of carbon atoms,
particularly 2 or 3.
It will be seen that the reaction ocuring in step (a) results in
the production of vic-halohydrin together with bicarbonate and that
vic-halohydrin and bicarbonate are required in the reaction of step
(b). Accordingly the bicarbonate by-product and unreacted water
from step (a) may be used to provide the aqueous medium required in
step (b) and in these circumstances, if steps (a) and (b) are
carried out consecutively to produce oxirane compound and/or glycol
from an olefinically unsaturated compound, the product mixture from
step (a) may advantageously be utilizing directly in step (b),
there being no need to separate the vic-halohydrin. Thus, for
example, the product mixture from step (a) may be fed directly to a
contacting device, for example a reaction and stripping column
(with or without the addition of more water) where step (b) is
carried out.
In order to obtain good yields of vic-halohydrin and to reduce the
possibility of undesirable by-products being produced, step (a)
should be carried out at a relatively low temperature and at a
relatively low concentration of hypohalite. Thus, step (a) is
preferably carried out at a temperature below 10.degree.C, although
of course it is desirable to maintain the reaction mixture above
its freezing point. In particular, operation at a temperature in
the range from -15.degree.C to +10.degree.C, especially from
+5.degree.C to +10.degree.C is generally preferred. The
concentration of hypohalite used in step (a), is preferably not in
excess of about 6 wt percent and most preferably lies in a range
from 2 to 5 wt percent. The contacting can conveniently be carried
out by transferring the aqueous solution to a contacting device
such as a distributer or packed column and introducing the carbon
dioxide and olefinically unsaturated compound into the device,
preferably in the form of an equimolar mixture since this satisfies
the stoichiometry of the reaction.
The reactions occuring in step (a) are assisted by operation at a
relatively high system pressure, whereas the reactions occuring in
step (b) are assisted by relatively low pressures. Thus step (a) is
preferably carried out at superatmospheric pressure, for example in
the range from 1.5 to 5.0 Kg/cm.sup.2 absolute and step (b) at a
pressure of from 0.5 to 2.0 Kg/cm.sup.2 absolute.
Step (b) is generally carried out at a higher temperature than step
(a), and preferably at a temperature in the range of 50.degree.C to
115.degree.C. Operation towards the higher end of this temperature
range, for example in the region of 115.degree.C, tends to result
in hydrolysis of oxirane compound to vic-glycol and, furthermore,
available evidence suggests that high concentrations of
bicarbonate, for example concentrations in excess of the
stoichiometric quantity, tends to result in hydrolysis of oxirane
compound. Accordingly, if it is desired to produce an oxirane
compound as opposed to a vic-glycol it is desirable to carry out
step (b) using not more that the theoretical quantity of
bicarbonate and to remove the oxirane compound rapidly from contact
with hot aqueous bicarbonate solution. The removal of oxirane
compound may be assisted by stripping, for example by injecting
steam into the reaction mixture. The carbon dioxide formed as
co-product in step (b) can be used to help to strip the oxirane
compound and it has been found that the injection of additional
carbon dioxide and/or the injection of steam and/or olefinically
unsaturated compound corresponding to the oxirane compound also
assists in stripping the desired oxirane compound and reduces
back-reaction to vic-halohydrin or coproduction of glycol. The use
of olefinically unsaturated compound has been found to be
particularly advantageous in this respect.
In a process that is preferred for economic reasons, the hypohalite
is provided by electrolysis of an aqueous solution of metal halide.
Since metal halide is produced as a by-product of step (b), when a
metal bicarbonate is used in the step the aqueous solution of metal
halide may advantageously be derived from the product of step (b).
In fact it has been found that the product of step (b) is generally
remarkably free from contaminants likely to foul the electrodes
used for, or otherwise interfere with, the electrolysis and it is
believed that the presence of trace remnants of hypohalite in the
product of step (a) assists in maintaining this freedom from
contaminants by oxidizing potentially harmful substances. The
presence of oxirane compound and/or vic-glycol is not considered to
be disadvantageous when carrying out the electrolysis, but it is
desirable to remove at least part thereof. Also carbon dioxide
produced in step (b) may be recycled to step (a) towards providing
at least a portion of, and preferably substantially all of the
carbon dioxide requirement of that step so that the only additional
requirement for carbon dioxide is as make-up for unavoidable
losses.
The concentration of the aqueous metal halide solution subjected to
electrolysis is preferably maintained at a relatively low level and
preferably less than 27 percent by weight to assist in providing a
satisfactory concentration of metal hypohalite for use in step (a).
On the other hand, too low a concentration of metal halide may
result in the undesirable evolution of oxygen during the
electrolysis and it has been found that a concentration in the
range from 15 to 27 percent by weight is generally
satisfactory.
The electrolysis usually results in the conversion of only a
portion of the metal halide to metal hypohalite and the product of
the electrolysis therefore generally comprises an aqueous solution
containing both metal halide and metal hypohalite. There is no need
to effect a separation of the metal hypohalite prior to carrying
out step (a) and this is a particularly advantageous feature of the
use of electroysis to produce the metal hypohalite. Also the
vic-halohydrin produced in step (a) is believed to be stabilized by
the presence of halide ions.
It will be seen that by recycling the carbon dioxide and metal
halide it is possible to set up a cyclic process for producing an
oxirane compound and/or vic-glycol from an olefinically unsaturated
compound, in which the only additional reagents required are water
(which in effect provides the oxygen of the oxirane compound and
the hydroxyl groups of the vic-glycol) and make-up quantities of
carbon dioxide and metal halide. In addition it is possible to
operate the process without the production of large quantities of
noxious effluents.
Thus according to a further aspect of the present invention there
is provided a process for converting an olefinically unsaturated
compound to an oxirane compound and/or a vic-glycol which comprises
the steps of:
i. forming an aqueous solution containing a metal hypohalite by
electrolysis of an aqueous solution of metal halide;
ii. intimately contacting an olefinically unsaturated compound and
carbon dioxide with aqueous solution containing metal hypohalite
formed in step (i) so as to form an aqueous solution of metal
bicarbonate and vic-halohydrin;
iii. maintaining metal bicarbonate and vic-halohydrin formed in
step (ii) in contact with one another under conditions of
temperature resulting in reaction to form an oxirane compound
and/or vic-glycol together with metal halide, carbon dioxide and
water;
iv. separately recovering carbon dioxide, an aqueous solution of
metal halide and a product stream comprising oxirane compound
and/or vic-glycol from the product mixture formed in step
(iii);
v. recycling carbon dioxide from step (iv) for use in step (ii) and
(vi) recycling aqueous metal halide solution from step (iv) for
electrolysis in accordance with step (i).
Preferred conditions for carrying out the above process are now
described.
Step (i)
An aqueous solution of a metal halide (for example sodium chloride)
having a concentration in the range from 15 to 27 wt percent is
electrolysed at a temperature of from -20.degree.C to +5.degree.C
in an electrolytic cell of the recirculation type under conditions
to yield a dilute solution containing up to 6 wt percent and
preferable from 2 to 5 wt percent of metal hypohalite in an aqueous
solution of the metal halide.
The overall reaction (as illustrated by the electrolysis of sodium
chloride) is as follows:
NaCl + H.sub.2 O .sup.Electrical Energy NaOCl + H.sub.2
The hydrogen evolved is led away and may be compressed prior to
disposal as a valuable by-product of the process.
Step (ii)
The aqueous metal hypohalite solution from step (i) may then be
pumped to a contacting device, for example a distributor or packed
column where it is reacted with an excess of a preferably equimolar
mixture of carbon dioxide and an olefinically unsaturated compound
(for example ethylene or propylene) at a low temperature of, for
example, from -5.degree. to +10.degree.C for a time sufficient for
reaction to take place. The reaction may be illustrated as follows
(R is for example H or CH.sub.3): ##SPC3##
By carrying out the reactions under the conditions referred to
above, substantially no byproducts such as dichloroalkanes and
dichloroalkyl ethers are produced and the reaction takes place to
near completion yielding a product containing equimolar quantities
of halohydrins and metal bicarbonate, for example sodium
bicarbonate, in a metal halide solution.
The excess carbon dioxide and olefinically unsaturated compound
(for example propylene or ethylene) may be compressed and recycled
after scrubbing in a tower with chilled water. The feed of
olefinically unsaturated compound may be introduced into this
recycle. Any inerts in the olefinically unsaturated compound may be
vented at an appropriate point in the recycle.
Step (iii)
The product from Step (ii) comprising an equimolar mixture of
halohydrins and metal bicarbonate in aqueous halide solution may
then be pumped to a reaction and stripping column where oxirane
compound is produced by the overall reaction: ##SPC4##
In order to carry out this reaction efficiently and to strip the
epoxide formed as soon as it is formed, the following procedures
and conditions may be adopted:
The system temperature is maintained in the range of 50.degree.C to
115.degree.C.
The system pressure is less than 3 atmospheres and preferably in
the range from 0.5 to 2 Kg/cm.sup.2 absolute.
Stripping agent such as carbon dioxide in addition to that produced
in situ in the course of the reaction and/or olefinically
unsaturated compound and/or steam may be employed to drive out the
epoxide more or less rapidly.
The feed to the reaction and stripping column may be diluted with
water.
Steps (iv) and (v)
The epoxide stripped out in Step (iii), which contains carbon
dioxide and olefinically unsaturated compound (when the latter is
used for stripping), may then be fed to a distillation column from
which pure oxirane compound may be taken as a side-stream well
below the top of the column. The overhead gases containing some
oxirane compound, carbon dioxide and olefinically unsaturated
compound (when the latter is used in stripping) may join the carbon
dioxide and olefinically unsaturated compound from step (ii) and
proceed to the water scrubbing tower referred to in Step (ii)
above, where the oxirane compound is absorbed in chilled water. The
scrubbed carbon dioxide and olefinically unsaturated compound (if
present) are recycled to Step (ii). The absorbate containing
oxirane compound may be continuously returned to the distillation
column, which preferably operates at near total reflux, the reflux
being provided by a refrigerant condenser operating at -10.degree.
to -30.degree.C. Reboil heat to the column may be supplied by low
pressure steam in a closed or open system.
Step (vi)
The bottom product of Step (iii), which consists of an aqueous
solution of metal halide with minimal content of impurities is
recycled back to Step (i). If dilution with water as described
above is effected, such water may be removed if desired, preferably
by freezing, before the salt solution proceeds to the electrolytic
cell of Step (i). If such dilution is not effected, the salt
solution can simply be cooled to the temperature required in Step
(i). The net feed to the electrolytic cell of Step (i) is, in
effect, the stoichiometric amount of water used up for the
production of one atom of oxygen per molecule of oxirane compound
produced .
The process of the invention will now be described by way of
example with particular reference to the accompanying drawing which
illustrates a flow sheet of apparatus suitable for converting an
olefinically unsaturated compound, for example ethylene or
propylene, to the corresponding oxirane compound.
Referring to the drawing, 10 represents an electrolytic cell, for
example, of the Krebs type, 11 represents an absorption column, 12
represents a saponifier, 13 represents a distillation column, 14
represents a freezing unit, for example of the Zarchin-Colt type,
and 15 represents a recycle gas scrubber.
In use of the apparatus, an aqueous solution of metal halide is
subjected to electrolysis at a temperature of from -5.degree. to
+10.degree.C in cell 10 to convert a portion of the metal halide to
metal hypohalite. The resulting aqueous solution containing metal
halide and metal hypohalite is pumped via line 16 to absorption
column 11 where it is contacted with a gaseous mixture of carbon
dioxide and olefinically unsaturated compound introduced via lines
17 and 18. Additional olefinically unsaturated compound may be
introduced into the absorption column via lines 19 and 20.
The temperature in the absorption column is maintained in the range
from -5.degree. to +10.degree.C, for example at about
+5.degree.C.
Hydrogen is formed as a by-product in the electrolytic cell and
passes via line 21 for compression and storage.
The gaseous effluent from the absorption column passes via lines 22
and 23 to the recycle gas scrubber, and the liquid effluent from
the absorption column, which comprises water, metal halide, metal
hypohalite, metal bicarbonate and vic-halohydrin corresponding to
the olefinically unsaturated compound is pumped via lines 24 and 25
to saponifier 12. A portion of the liquid effluent is diverted
along line 26 to the recycle gas scrubber 15. Saponifier 12 is
operated at a temperature above 10.degree., for example in the
range from 50.degree. - 115.degree.C and the contents are
maintained at this elevated temperature by withdrawing a liquid
stream in line 27 and diverting a portion through a steam-heated
recycle loop 28. The remainder of the stream withdrawn in line 27
is pumped through line 29 which includes a cooler 30 and a portion
of the cooled stream is recycled via line 31 to the top of
saponifier 12 to act as a reflux. The remainder of the cooled
stream is returned via lines 34 and 35 to the freezing unit 14.
As described above, the metal bicarbonate and vic-halohydrin react
in the saponifier 12 to form oxirane compound, carbon dioxide,
metal halide and water. The carbon dioxide evolved assists in
stripping the oxirane compound, and the carbon dioxide and oxirane
compound pass together as a gaseous stream via line 32 to
distillation column 13.
In order to enhance the stripping of the oxirane compound from the
contents of saponifier 12, olefinically unsaturated compound may be
injected at the bottom of the saponifier via lines 19 and 33.
Distillation column 13 is operated at near total reflux using a
refrigerated condensor in a reflux loop comprising lines 37 and 38.
The overhead product gases are passed via lines 39 and 23 to
recycle gas scrubber 15. The distillation column reboil heat is
supplied by low pressure steam in a closed or open system
represented by line 40. Oxirane compound is removed as a
side-stream 41 at a point well below the top of the column and the
column bottoms, comprising mainly water, are passed via lines 42
and 29 to join the cooled stream in lines 34 and 35. Excess water
may be bled from the system via line 43 and make-up water (which
may contain metal halide as required) may be introduced into the
system via line 44.
The combined stream in line 35 comprises aqueous metal halide which
is concentrated as required in freezer 14, the concentrated metal
halide solution passing via line 45 to electrolytic cell 10 and a
portion of the water separated in the freezer is pumped via lines
46 and 26 to join the liquid effluent flowing into saponifier 12
via line 25. The remainder of the water passed along line 52 to the
top of the recycle gas scrubber, is used to scrub the gaseous
effluent passing to the scrubber via line 23. If desired the
quantity of water passing along line 26 may be reduced or
eliminated by closing valve 51.
The bottoms from the recycle gas scrubber contain oxirane compound
which is passed to distillation column 13 via line 47. The scrubber
gases comprising carbon dioxide and olefinically unsaturated
compound are passed to absorption column 11 via line 17 and 18 as
described above, olefinically unsaturated compound and make-up
carbon dioxide being introduced into the system via lines 48 and 49
and waste gases being vented via line 50.
A typical mass balance for the apparatus described is given in the
following Table, which relates to the production of propylene oxide
from propylene using sodium hypohalite as oxidant.
LINE 45 16 24 25 32 34 COMPONENT TIME Ion/Hr Wt% Ton/Hr Wt% Ton/Hr
Wt% Ton/Hr Wt% Ton/Hr Wt% Ton/Hr Wt%
__________________________________________________________________________
Propylene Oxide -- -- -- -- -- -- -- -- 1.53 37.10 -- -- Propylene
Chlorhydrin -- -- -- -- 2.59 4.65 2.59 2.46 -- -- -- -- Sodium
Chloride 9.06 17.00 7.46 14.00 7.46 13.40 7.46 7.07 -- -- 9.06 8.81
Sodium Hypochlorite -- -- 2.04 3.83 -- -- -- -- -- -- -- -- Sodium
Bicarbonate -- -- -- -- 2.30 4.13 2.30 2.18 1.21(CO.sub.2) 29.40 --
-- Water 44.27 83.00 43.78 82.17 43.29 77.82 93.29 88.29 1.38 33.50
93.78 91.19
__________________________________________________________________________
TOTAL 53.33 100.00 53.28 100.00 55.64 100.00 105.64 100.00 4.12
100.00 102.84 100.00
__________________________________________________________________________
This mass balance assumes a quantity of water of 50 tons/hour
flowing in line 26 and entering saponifier 12 through line 25,
however this could be reduced or omitted altogether. In such
circumstances, it would also be possible to omit the freezer unit
14, in which case the stream withdrawn in line 27 from the bottom
of the saponifier could be recycled directly back to the
electrolysis cell.
The production of ethylene oxide and propylene oxide in accordance
with the invention will now be described by way of example.
EXAMPLE 1
A. chlorhydrin production
An equimolar mixture of carbon dioxide and propylene was passed
into an aqueous solution containing 14 percent by weight of sodium
chloride and 4 percent by weight of sodium hypochlorite, which was
maintained at a constant temperature, which was varied in the range
of -15.degree.C. to + 10.degree.C. during a series of experiments.
The reaction was followed by withdrawing from time to time a few
drops of the reaction mixture and testing with an acidified
solution of potassium iodide. The reaction was continued until no
iodine was liberated, and the total time noted.
The volume of the reaction product was measured and an aliquot part
was neutralized with hydrochloric acid, and extracted with ether.
The extract was evaporated free of ether, dried and weighed. The
chlorhydrins so obtained were then subjected to analysis by
chromatography and infra-red spectroscopy.
The yields of the mixed chlorhydrins (1 chloro-2-propanol and
2-chloro-1-propanol), based on the sodium hypochlorite used were as
follows:
Temperature Reaction Time Yield
______________________________________ -10.degree.C. 40 minutes 82%
0.degree.C. 33 minutes 96% 5.degree.C. 22 minutes 94%
______________________________________
B. conversion to oxirane
A portion of reaction product from Step A was charged into a
reaction vessel fitted with a condenser which was connected to two
cold traps in series at -40.degree.C. and -80.degree.C. Stirring
was effected mechanically and also by the bubbling of carbon
dioxide into the solution. The vessel and its contents were heated
very quickly to the reaction temperature, which, in a series of
experiments, ranged from 50.degree.C. to 115.degree.C.
Samples were withdrawn from time to time and analyzed by titration
for unreacted sodium bicarbonate in the solution and for propylene
oxide collected in the cold traps by chromatography.
The yields of propylene oxide, based on the propylene chlorhydrin
in the charge, varied from 70 percent to 94 percent in the
temperature range of 50.degree.C. to 115.degree.C. with approximate
reaction times in the order of 50 minutes to 15 minutes.
EXAMPLE 2
Example 1 was repeated using ethylene instead of propylene, the
same procedures being followed. The yield of ethylene chlorhydrin,
based on the sodium hypochlorite used, was 95 percent at
0.degree.C. and a reaction time of 30 minutes.
The yield of ethylene oxide, based on the ethylene chlohydrin
charged to the vessel varied from 80 percent to 95 percent in the
temperature range of 50.degree.C. to 115.degree.C, with approximate
reaction times in the order of 60 minutes to 20 minutes.
A particular advantage of the process described herein is that a
single apparatus (for example the apparatus described and
illustrated herein) may be used without substantial modification
for the production of both ethylene oxide from ethylene and
propylene oxide from propylene.
Furthermore the process does not involve the handling of free
halogen or alkali and accordingly the problems of corrosion
encountered with these materials do not arise. The process can be
operated with efficient utilization of reagents and the oxygen
required in forming the oxirane compounds or vic-glycols is in
effect derived from water and thus may be obtained cheaply. Also
high purity hydrogen is produced as a by-product of the process
which may be sold, thus improving the overall economics of the
process. It should be noted that the process described results in
the production of substantially no noxious effluent likely to
pollute the environment and that the impurity content of the metal
halide solution produced as a result of the reaction between
aqueous metal bicarbonate and chlorhydrin is generally not high
enough to foul the electrolytic cell used to produce metal
hypohalite.
* * * * *